金属卟啉的合成及其对细胞色素P-450的模拟 12.μ-氧-双铁(Ⅲ) 卟啉系列化合物对环已烷的单充氧催化物作用

研究了九种μ-氧-双四苯基卟吩合铁(Ⅲ)]衍生物TXPPPe^Ⅲ]~O 在温和条件下PHIO环已烷氧化成环以醇和环已酮的反应,结果表明,该反应的产率和速率与卟啉环上取代基的特性常数之间存在的线性关系, 反应的产物分布和动力学性质与反应温度,溶剂型质以及空气有关,还考察了这一反应过程的另一竞争反应-氧化剂对 TXPPEeⅢ~O的破坏反应,根据文献报道和实验结果,本文对μ-氧-双铁(Ⅲ)卟啉催化环已烷羟基化反应的可能途径进行了探讨.

Synthesis of porphyrin compounds and their imitation for cytochrome P-450. 12.μ-Oxo-bisiron(Ⅲ)porphyins-catalyzed monooxygenation of cyclohexane

The hydroxylation of hydrocarbon with PhIO catalyzed by nine derivatives of substituted m-oxo-bis-iron(III) porphyrins under room temperature and atomsphere is studied. It is shown that there exists a linear relationship between the rate constants of the reactions and the constants of substituents on porphyrin ring. The product distributions and kinetic properties of the reactions are found to be dependent on the reaction temperature, solvent as well as the atomsphere Meanwhile, the oxidation of these porphyrins with PhIO, a reaction contending with the hydroxylation, is also studied.